Process for preparing a liquid detergent composition



United States Patent assignors to Swift & Company, Chicago, 111., a corpora-- tion of Illinois No Drawing. Filed Nov. 24, 1961, Ser. No. 154,869 Claims. (Cl. 252117) This invention relates to the preparation of an improved detergent product. More particularly, the invention has to do with the preparation of an improved detergent mixture having important properties and containing the reaction products of an alkylol amine, a polyprotic acid such as phosphoric, fatty acids containing about 8-10 carbons and an acylating substance.

One embodiment of this invention involves the preparation of complex mixtures of surface-active materials from natural products containing fats and oils. This invention enables the utilization of inexpensive fats and oils in large quantities. The process of treating such materials and the valuable products obtained provide a means for upgrading low-priced fats or fatty acids such as tallow, grease, acidulated vegetable oil foots or still bottoms. Also, the relatively cheap C C fatty acids are used.

Derivatives of amino alcohols have been proposed heretofore as detergents and in other are-as of use where compositions having the ability of altering surface properties of liquids and solids are required. The compositions of this invention, while derivatives of amino alcohols, provide many advantages not exhibited by previously known amino alcohol derivatives.

The compositions, irrespective of the particular alkylolamine or acylating substance, possess the property of modifying surface behavior of liquids in which they are incorporated. This modification of surface behavior is observed in aqueous solutions containing large quantities of electrolytes. This is an important advantage when it is realized that the majority of .previously known amino alcohol derivatives are not compatible with aqueous solutions containing more than small amounts of electrolytes. These solutions tend to salt out many of the known alkylolamides resulting in a substantial reduction in effectiveness of these compositions. Moreover, the normally used detergents have limited solubility in the presence of electrolytes which results in an impaired detergent action. On the other hand, the compositions of this invention are quite soluble in such electrolytes. The coconut oil detergent, for example, is used in wool fulling when there is present a high soda ash concentration.

It is an object of this invention to provide new chemical compositions.

Another object is the provision of a method for the utilization of inexpensive fats and oils in large quantities.

Another object is to provide detergents which will function satisfactorily in high concentrations of electrolytes.

Additional objects, if not specifically set forth herein, will be readily apparent to those skilled in the art from the detailed description of the invention which follows.

The liquid detergent compositions of this invention are prepared by heating together (with agitation under vacuum at a temperature of about 280 to 360 degrees R, 285-305 degrees preferred, for about 2 to 4 /2 hours) a mixture of (1) an alkylol amine, (2) an acylating substance, (3) C3-C10 fatty acids or their alkyl esters, and (4) an inorganic acid. The mixture is usually heated until most of the volatile products come off.

A neutralizing agent such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, potassium carbonate, sodium carbonate, or ammonia is added and the 3,250,718 Patented May 10, 1966 batch is agitated for around fifteen minutes to one-half hour at a temperature of about -470 degrees F. Then more acylating substance is added to form a soap.- Water and a miscible solvent are added and agitate d for another half-hour or so to reduce the viscosity of the finished composition.

The alkylolamines are usually employed in an excess (1 to 10 moles per 1 equivalent of fatty acids) and react with the fatty acids to form alkylol amides which in turn are reacted with the inorganic acid to form what is believed to be esters. In the case of phosphoric acid enough is added to make the product soluble and a phosphate-ester linkage is believed to be formed. The unreacted acid is neutralized with a base such as sodium hydroxide. A soap is formed by adding additional acylating fatty acids to the unreacted amine present in the reaction mixture. The .purpose of the solvent and Water is to provide the desired viscosity and concentration.

The compositions of this invention are believed to be compounds comprising aliphatic amide alcohols bridged by means of an ester linkage such as a phosphate-ester. The actual structure appears to be immaterial, however, as long as the phosphoric acid is attached. Considerable variation in structure of the composition is possible inasmuch as any of a large number of acyl groups may be present in the alkylol amide and any of a number of alkylol amines may be employed in the alkylol amine portion of the mixture. Similarly, diverse combinations of alkylol amine radicals may be present in the alkylol amine and alkyl-o1 amide portions of the mixture.

More specifically, the compositions are complex mixtures obtained by reacting primary, secondary, or tertiary alkylol amines, and fatty alkylolamides with a polyprotic acid such as phosphoric.

Polyprotic acids are meant to be those which contain and HO group attached to the nonmetal portion and may or may not contain an 0 group. Polyprotic acids are also meant to cover the alkyl esters thereof. For example l ROPOR, S|OR OR OR and Amin'o alcohols which may be used include primary,

secondary, and tertiary amino aliphatic alcohols. The lower alkylol amines of two to eight carbon atoms are very satisfactory, but higher alkylol amines can also be used. Typical alkylol amines which may be reacted with the inorganic acid are monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N,N-dimethylethanolamine, N-ethyl, N-

hexylethanolamine, N,N-diisopropyl ethanolamine, etc.

The amino alcohols may also be diamino compounds and may be unsubstituted or substituted with noninterfering substituents.

The acylating substances used in this invention are the fixed fats and oils. The fatty acids which are taken from the animal and vegetable oils can be straight chain, branched chain, saturated and unsaturated such as caprylic, stearic, palmitic, oleic, linoleic, lauric, etc. One of the main features of this invention is the utilization of inexpensive fats and oils in large quantities. Tall oil, crude or refined, which contains minor amounts of rosin acids; or any low-priced fat or fatty acid such as tallow, grease, acidulated vegetable oil foots or still bottoms may be used. Other examples include butter, mutton tallow, castor oil, olive oil, palm oil, coconut oil, peanut oil, corn oil, cottonseed oil, linseed oil, red oil, soybean oil, tung oil, etc. The fatty acyl portion usually contains 4-26 carbons and may be unsubstituted or substituted with non-interfering substituents. A mixture of the fatty acids 'wherein at least some C unsaturated acids are present is preferred along with acids in the range of C C The other acylating ingredient is a fatty acid of about 8-10 carbons or a mixture of any combination of C C fatty acids or their esters. Specific examples include a 50-50 mixture of methyl icaprylate and capricate, and mixtures of methyl, ethyl, propyl, butyl, etc., esters of pelargonic acid. The lower esters or the free (I -C fatty acids are preferred due to their relatively cheap cost. Pel-argonic acid is a specific preferred ingredient.

Preferred solvents which may be used to reduce vis-' cosity of the composition are diethylene glycol monoethyl ether, ethyl alcohol, methyl alcohol, isopropyl alcohol, glycerine, propylene glycol, ethylene glycol monobutyl ether, or other H O miscible solvents.

The constituents can usually be varied in the amounts stated below:

(9) Water As can be seen from the above table, the amounts of ingredients can vary greatly. Generally, however, the composition should contain the (l -C and C C acids in a combination total of at least 10-20%.

The following examples are given to illustrate the invention. It will be understood, however, that these examples are illustrative and not to be taken in any manner as limiting the invention as defined in the appended claims.

Example I 180 grams of diethanolamine, 58 grams of tall oil fatty acids (3-5% rosin acids), 22 grams of methyl esters of caprylic and capric acids (a 50-50 mixture) and 23.4 grams of phosphoric acid (85%) are heated together in a reactor with agitation under vacuum of 3-5 inches of mercury at a temperature of 310 to 320 F. After a period of heating for 3 /2 to 4 /2 hours, the temperature is raised to 340 to 345 F. and is maintained at this level for a period of 1% to 2 hours. The temperature is then lowered to 140 F.-170 F. and 30 grams of aqueous sodium hydroxide'(11%) is added and the batch is agitated for minutes to /2 hour. Then 60 grams of tall oil fatty acids, grams of coconut oil fatty acids, 22.2 grams of solvent (diethylene glycol monoethyl ether) and 44.5 grams of water are added in this order and the batch agitated for another half hour, at which time manufacturing of the composition is complete.

The temperatures, times and the vacuum disclosed above are important for the manufacture of this specific material.

The use of the free C -C acids in place of the esters of captrylic and capric in the above example eliminates the problem of methyl alcohol recovery. The alcohol which is freed, being volatile, will come off and should be collected. Also the amount of foaming is decreased when the free acids are used.

As mentioned above, the use of coconut oil fatty acids as the acylating agent results in a product having outstanding properties in that it will function in a satisfactory manner in wool fulling Where there is a high electrolyte concentration.

An example of the procedure to form the coconut detergent is as follows:

Example II Dietl'ranolamine (420 g.), coconut oil fatty acids (132.5 g.), pelargonic acid (51.6 g.), and 54.8 g. of 85% phosphoric acid are heated together in a reactor with agitation under 28 inches of vacuum and reacted for around 2% hours at about 300 F. The clear amber mixture is cooled under vacuum for clear color. The mixture is cooled to around 140 F. and 70 g. of 11% sodium hydroxide is added and agitated for around A to /2 hour. After the NaOH has been thoroughly mixed into the batch, 186.8 g. of additional coconut oil fatty acids is added to form a soap. The solution becomes thicker on addition of the coconut oil fatty acids, and 81.6 g. of diethylene glycol monoethyl ether is added to provide the desired viscosity.

Example III p G. Diethanolamine 290 Refined tall oil fatty acids 93.5

Mixture of lower alkyl caprylate and 'capricate or pelargonate 33.5 85% H PO 35.4 11% NaOH 96.7 Refined tall oil fatty acids 192.9 Coconut oil fatty acids 64.5 Diethylene glycol monoethyl ether 64.5

The procedure is the same as Example II, and 290 grams monoethanolamine was also substituted for the diethanolarnine. The above example was also carried outdwith red oil (oleic acid) replacing all the tall oil fatty aci s.

Example IV Diethanolamine 392.0

Coconut oil 126.5

Mixture of methyl esters of capric and caprylic acids 48.0 85% phosphoric acid 50.8 11% sodiumhydroxide 65.5

Coconut oil 130.0

Coconut oil fatty acids 43.0 Diethylene glycol monoethyl ether 47.5 Water 97.1

The procedure is the same as Example II, and pelargonic acid can be substituted for the methyl esters and monoisopropanolamine for diethanolamine.

Example V 11% sodium hydroxide is added and the mixture is agitated for about one half hour. After the NaOH has been thoroughly mixed into the batch, 42.8 grams of coconut oil and 14.4 grams of coconut oil fatty acids are added to form a soap. In order to reduce the viscosity of the finished composition, 15.5 grams of diethylene glycol monoethyl ether and 31.7 grams of water are added.

It will be appreciated that the details and examples hereinbefore set forth are illustrative only and are in no Way to be considered as limitations of the invention.

-We claim:

1. A process for preparing an improved liquid detergent which comprises simultaneously reacting at an elevated temperature and under vacuum (1) a stoichiometric excess of an alkylolamine having about 2 to 8 carbon atoms per alkylol group, (2) a member selected from the group consisting of ternary polyprotic inorganic acids and the C -C alkyl esters thereof, said ternary polyprotic inorganic acid consisting of hydrogen, oxygen and a member selected from the group consisting of sulphur, phosphorus and boron, and (3) an aliphatic fatty acylating substance containing 4 to 26 carbons in the acyl portion thereof, said aliphatic fatty acylating substance containing C C and C C aliphatic fatty acylating substances in an amount of at least about 10%, by weight, based upon the total weight of ingredients (1), (2), and (3).

2. A process for preparing an improved liquid detergent which comprises simultaneously reacting at a temperature above about 280 F. and under vacuum (1) a stoichiometric excess of an alkylolamine having about 2 to 8 carbon atoms per alkylol group, (2) a member selected from the group consisting of ternary polyprotic inorganic acids and the C -C alkyl esters thereof, said ternary polyprotic inorganic acid consisting of hydrogen, oxygen and a member selected from the group consisting of sulphur, phosphorus and boron, (3) a C C aliphatic fatty acid, and (4) a member selected from the group consisting of C -C fatty acids, the lower alkyl esters of said C -C fatty acids and mixtures thereof.

3. A process for preparing an improved liquid detergent which comprises simultaneously reacting at a temperature between about 280 F. and 360 F. and under vacuum (1) about 25 to 60%, by weight, of an alkylolamine having about 2 to 8 carbon atoms per alkylol group, (2) about 1 to 20%, by weight, of a member selected from the group consisting of fixed fats and oils having free aliphatic fatty acids, the acyl portion of said fixed fats and oils and said free aliphatic fatty acids having about 4 to 26 carbon atoms, (3) about 1 to 20%, by weight, of a member selected from the group consisting of C -C fatty acids, the lower alkyl esters of said C C fatty acids and mixtures thereof, and (4) about 1 to 15%, by weight, of a member selected from the group consisting of ternary polyprotic inorganic acids and the C -C alkyl esters thereof, said ternary polyprotic inorganic acid consisting of hydrogen, oxygen and a member selected from the group consisting of sulphur, phosphoru and boron.

4. A process for producing an improved liquid deterbent which comprises heating to a temperature between about 280 F. and 360 F. and simultaneously reacting under vacuum (1) a 1 to 10 mol excess per equivalent of fatty acids of an alkylolamine having 2 to 8 carbon atoms per alkylol group, (2) a member selected from the group consisting of ternary polyprotic inorganic acids and the C -C alkyl esters thereof, said ternary polyprotic in organic acid consisting of hydrogen, oxygen and a member selected from the group consisting of sulphur, phosphorus and boron, (3) an aliphatic fatty acid having 12 to 26 carbon atoms, and (4) a member selected from the group consisting of C C fatty acids, the lower alkyl esters of said C C fatty acids and mixtures thereof, cooling the reaction mixture and thereafter reacting said mixture with an aliphatic fatty acid having from 8 to 26 carbon atoms whereby said excess alkylolamine reacts with said fatty acids having 8 to 26 carbon atoms to form soaps.

5. A process for preparing an improved liquid detergent which comprises simultaneously reacting, at a temperature between about 310 F. to 320 F. with agitation under vacuum for about 3 /2 to 4 /2 hours, a mixture in the ratio of about 180 grams of diethanolamine, about 58 grams of tall oil fatty acids, about 22 grams of the methyl ester of caprylic acid and capric acid, and about 23.4 grams of phosphoric acid; raising the temperature of said mixture to about 340 F. to 345 F. and maintaining said temperature for about 1 /2 to 2 hours; lowering the temperature of said mixture to about F. to F.; adding to said mixture about 30 grams of 11% aqueous sodium hydroxide, about 60 grams of tall oil fatty acids, about 20 grams of coconut oil fatty acids, about 22.2 grams of diethylene glycol monoethyl ether, and about 44.5 grams of water and agitating the mixture for about /2 hour.

References Cited by the Examiner UNITED STATES PATENTS 2,089,212 8/1937 Kritchevsky 260404 XR 2,545,357 3/1951 Jayne 252-137 2,586,496 2/1952 Young et a1. 252-1 17 2,607,740 8/1952 Vitale et a1 252117 XR JULIUS GREENWALD, Primary Examiner I. T. FEDIGAN, Assistant Examiner. 

1. A PROCESS FOR PREPARING AN IMPROVED LIQUID DETERGENT WHICH COMPRISES SIMULTANEOUSLY REACTING AT AN ELEVATED TEMPERATURE AND UNDER VACUUM (1) A STOICHIOMETRIC EXCESS OF AN ALKYLOLAMINE HAVING ABOUT 2 TO 8 CARBON ATOMS PER ALKYLOL GROUP, (2) A MEMBER SELECTED FROM THE GROUP CONSISTING OF TERNARY POLYPROTIC INORGANIC ACIDS AND THE C1-C8 ALKYL ESTERS THEREOF, SAID TERNARY POLYPROTIC INORGANIC ACID CONSISTING OF HYDROGEN, OXYGEN AND A MEMBER SELECTED FROM THE GROUP CONSISTING OF SULPHUR, PHOSPHORUS AND BORON, AND (3) AN ALIPHATIC FATTY ACYLATING SUBSTANCE CONTAINING 4 TO 26 CARBONS IN THE ACYL PORTION THEREOF, SAID ALIPHATIC FATTY ACYLATING SUBSTANCE CONTAINING C8-C10 AND C12-C18 ALIPHATIC FATTY ACYLATING SUBSTANCES IN AN AMOUNT OF AT LEAST ABOUT 10%, BY WEIGHT, BASED UPON THE TOTAL WEIGHT OF INGREDIENTS (1), (2), AND (3). 